Di-(aryloxy)-methanes



Patented Oct. 17, 1950 I I "DI:(ARYLOXY)-METHANES- V Edgar. C. Britten-and Ezra Monroe, Midland, and

Clare It Hand, Sanford, Mich, assign'ors to The Dow Chemical Company, Midland, Micha corporation of Delaware N Drawing. Application .l 3,1948,

Serial No. 37,058

H 7' Qlainisr (01. 60413) t This invention is: directed" to di (aryloxy) methanes having the following formulai Y wherein one X is hydrogen and the otherX is a lower alkyl radical containing from '1 to 4 carbon atoms; inclusive. Membersofthis group'of compounds have been prepared and. found to be useful as insecticides; and as intermediates in the preparation of more complex organic derivatives. The compounds are oils or crystalline solids, somewhat soluble in ina'r1y 'organimzfsolv nts and substantially insolublein water. v f

' The new compounds maybe prepared byreacting an alkali metal phenolate with a methylene halide such as dichloro-methane or dibromomethane. The sodium phenolates are preferably employed. In carrying out the reaction, equimolecular proportions of sodium hydroxide and the substituted phenol are dissolved in methyl or ethyl alcohol. A one-half molecular proportion of the methylene halide is then, added to the mixture and the latter heated under autogenous pressure to 'a temperature of between 90 and 140 C. for a period'of time required to complete the reaction. The reaction mixture is then washed with water, and treated in conventional fashion to recover the product. crude reaction product may be purified by fractional distillation under reduced pressure, or in the case of a crystalline solid, by recrystallization from organic solvents. v

Example 1 168 grams (4.2 mols) of sodium hydroxide, 570 grams (4 mols) of 4-chloro-2-methy1-phenol, 173.3 grams (2.04 mols) of dichloro-methaneand 319 grams of methyl alcohol was heated in a pressure reactor with agitation at 120 to 135 C. for 11 hours. The crude reaction product was washed with water and recrystallized from methylene dichloride to obtain di-(4-chloro-- 2-methyl-phenoxy)-methane, a crystalline solid having a melting point of 146.5 to 148 C.

v Example 2 In a manner similar to that of Example 1,

570 grams (4 mols) of 6-chloro-2-methyl-phenol,

168 grams (4.2 mols) of sodium hydroxide, 173.3 grams (2.04 mols) of dichloro-methane and 319 grams of methyl alcohol were heated. in a pres- If desired, the

Water.

' grams'of di-'(j6-chlord-2-niethyl an'e as an' oil'y liquid havingla r'ejfractive' indexj.

sure reactor at a temperature of 112 to -"C. for 10 /4 hours. At the end of thisperi'odythe reactor and contents were cooled and the crude reaction mixture discharged into an excessof The organic products of reaction were recovered from the water dispersion by extraction with chlorob'enzene, and the washed benzene extract fractionally distilled under reduced pressure. From this fractionation was obtained 317 v "Emmet Similarly, 2-chloro f 4 r secondarybutyl phenol was reacted with dichloro-methane to obtain di-(2 chloro-4-seco ndarybutyl-phenoxy) -'nethane, an oily liquid" having a refractive index n/Dof 1.5479 at 25 C.

' Eicample 4 Di-(4 chloro 2 secondarybutyl phenoxy) methane was prepared by reacting 4-chloro- 2-secondarybutyl-phenol with dichloro-methane and found to be an oily liquid having a refractive index n/D of 1.5477 at 25 C.

Other compounds which may be similarly prepared include di-(4-chloro 2 methyl-phenoxy) methane, di-(4-chloro 2 propyl-phenoxy) -methane, di- (6-chloro-2-ethyl-phenoxy) methane, di (G-chloro-2-propylphenoxy) -methane, di-(6-chloro-2-butyl-phenoxy) -methane, di-

(2 chloro -4 methyl-phenoxy) -methane, di- (2 chloro 4 ethyl phenoxy) methane, di- (2 chloro 4 propyl phenoxy) -methane, di-', (3 chloro 4 methyl phenoxy) -nethane, di-

(3 chloro 4 ethyl phenoxy) methane, di-

(3 chloro 4 propyl phenoxy) -methane, di- (3 chloro 4 butyl phenoxy)-methane, di- (3 chloro 2 methyl-phenoxy) -methane, di" (3 chloro 2 ethyl phenoxy) -methane, di- (3-chloro 2 propyl phenoxy)-methane, di- (3 chloro 2 butyl phenoxy)-methane, di- (5-chloro 2 methyl phenoxy) -methane, di- (5 chloro 2 ethyl phenoxy) methane, di- (5-chloro-2-propyl-phenoxy) -methane and di- (5chloro-Z-butyl-phenoxy) -methane.

I We have found that the new compounds are effective as insecticides and may be employed in the dosages required. for insect control with negligible injury to the foliage of plants. In this use the compounds are preferably employed in combination with an inert carrier, They may be dispersed on a finely divided solid and employed as a dust mixture. Such mixture may be henoxyf meth The foregoing materials were mechanically mixed and the product subsequently dispersed in water to produce a spray containing 3 pounds of the toxicant per 100 gallons. When this composition Was applied against bean aphids on nasturtium plants and 2-spotted spider mites on cranberry bean plants a 100 per cent kill of the test organisms was obtained.

We claim: i

1. A di-(ary1oxy)-methane having the following formula:

wherein one X is hydrogen and the other X is a lower alkyl radical containing from 1 to 4 carbon atoms, inclusive.

2. A di-(aryloxy) -methane having the following formula:

-wherein X is a lower alkyl radical containing from 1 to 4 carbon atoms, inclusive.

3. A di-(aryloxy)-methane having the following formula:

wherein X is a lower alkyl radical containing from 1 to 4 carbon atoms, inclusive.

4. A di-(aryloxy) -methane having the following formula:

wherein X is a lower alkyl radical containing from 1 to 4 carbon atoms, inclusive.

5. Di- 6-chloro-2-methyl-phenoxy) methane. 6. Di-(4-chloro-2-secondarybutyl phenoxy) methane.

7. Di-(2-chloro-4-secondarybutyl phenoxy) methane.

EDGAR 0. BRITTON. EZRA MONROE. CLARE R. HAND.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name ,Date

2,130,999 Coleman et a1. Sept. 20, 1938 2,291,528 Bruson et al July 28, 1942 2,330,234 Moyle Sept. 28, 1943 

1. A DI-(ARYLOXY)-METHANE HAVING THE FOLLOWING FORMULA: 